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Both title compounds, bis[tris(2-aminoethyl)amine]nickel(II) dichloride, [Ni(tren)2]Cl2, (I), and bis[tris(2-aminoethyl)amine]nickel(II) tetrathiotungstate, [Ni(tren)2]WS4, (II), contain the [Ni(tren)2]2+ cation [tren is tris(2-aminoethyl)amine, C6H18N4]. The tren molecule acts as a tridentate ligand around the central Ni atom, with the remaining primary amine group not bound to the central atom. In (I), Ni2+ is located on a centre of inversion surrounded by one crystallographically independent tren molecule. In the [Ni(tren)2]2+ cation of (II), the Ni atom is bound to two crystallographically independent tren molecules. The Ni atoms in the [Ni(tren)2]2+ complexes are in a distorted octahedral environment consisting of six N atoms from the chelating tren molecules. The counter-ions are chloride anions in (I) and the tetrahedral [WS4]2- anion in (II). Hydrogen bonding is observed in both compounds.
Supporting information
CCDC references: 181978; 181979
[Ni(tren)2]Cl2, (I), was prepared in a 100 ml glass flask at room
temperature (293 K). NiCl2·6H2O (237.7 mg, 1 mmol) was dissolved in
ethanol (99%, 10 ml) and tren (95%, 10 ml) was added to the mixture. Violet
crystals were received after 48 h. The phase-pure product was washed with
ethanol and dried under vacuum. [Ni(tren)2]WS4, (II), was prepared under
solvothermal conditions. NiCl2·6H2O, Na2WO4·2H2O and
sulfur (0.50 mmol, molar ratio 1:2:8) were reacted in tris(2-aminoethyl)amine
(95%, 3 ml) in a Teflon-lined steel autoclave at 393 K for 5 d. The product
was filtered off and washed with water. The yield of the phase-pure product is
about 60%. The yellow–brown crystals obtained are stable on air.
The H atoms were positioned with idealized geometry and refined isotropically.
For both compounds, data collection: DIF4 (Stoe & Cie, 1992); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1992); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Crystal Impact, 1999); software used to prepare material for publication: CIFTAB in SHELXL97.
(I) 'bis[tris(2-aminoethyl)amine]nickel(II) dichoride'
top
Crystal data top
[Ni(C6H18N4)2]Cl2 | F(000) = 452 |
Mr = 422.10 | Dx = 1.439 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.0336 (18) Å | Cell parameters from 37 reflections |
b = 10.630 (2) Å | θ = 9–16° |
c = 10.717 (2) Å | µ = 1.28 mm−1 |
β = 108.78 (3)° | T = 293 K |
V = 974.3 (3) Å3 | Needle, violet |
Z = 2 | 0.5 × 0.1 × 0.1 mm |
Data collection top
STOE AED-II four-circle diffractometer | 1131 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.034 |
Graphite monochromator | θmax = 25.0°, θmin = 2.6° |
ω–θ scans | h = 0→10 |
Absorption correction: ψ scan X-SHAPE (Stoe & Cie, 1998) and X-RED (Stoe & Cie, 1998) | k = −12→1 |
Tmin = 0.810, Tmax = 0.840 | l = −12→12 |
2042 measured reflections | 4 standard reflections every 120 min |
1715 independent reflections | intensity decay: none |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.073 | Only H-atom coordinates refined |
S = 1.01 | Calculated w = 1/[σ2(Fo2) + (0.0306P)2] where P = (Fo2 + 2Fc2)/3 |
1715 reflections | (Δ/σ)max < 0.001 |
160 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
Crystal data top
[Ni(C6H18N4)2]Cl2 | V = 974.3 (3) Å3 |
Mr = 422.10 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.0336 (18) Å | µ = 1.28 mm−1 |
b = 10.630 (2) Å | T = 293 K |
c = 10.717 (2) Å | 0.5 × 0.1 × 0.1 mm |
β = 108.78 (3)° | |
Data collection top
STOE AED-II four-circle diffractometer | 1131 reflections with I > 2σ(I) |
Absorption correction: ψ scan X-SHAPE (Stoe & Cie, 1998) and X-RED (Stoe & Cie, 1998) | Rint = 0.034 |
Tmin = 0.810, Tmax = 0.840 | 4 standard reflections every 120 min |
2042 measured reflections | intensity decay: none |
1715 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.073 | Only H-atom coordinates refined |
S = 1.01 | Δρmax = 0.28 e Å−3 |
1715 reflections | Δρmin = −0.27 e Å−3 |
160 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ni | 0.0000 | 0.5000 | 0.5000 | 0.02336 (16) | |
Cl | 0.60984 (11) | 0.22982 (9) | 0.43273 (9) | 0.0475 (3) | |
N1 | 0.0988 (3) | 0.5908 (3) | 0.3655 (3) | 0.0313 (7) | |
H1N | 0.024 (4) | 0.621 (3) | 0.293 (3) | 0.038* | |
H2N | 0.155 (4) | 0.651 (3) | 0.403 (3) | 0.038* | |
N2 | 0.1686 (3) | 0.3570 (3) | 0.4910 (2) | 0.0268 (6) | |
N3 | 0.1847 (3) | 0.5603 (3) | 0.6654 (3) | 0.0291 (6) | |
H3N | 0.236 (4) | 0.623 (3) | 0.642 (3) | 0.035* | |
H4N | 0.158 (4) | 0.587 (3) | 0.731 (3) | 0.035* | |
N4 | 0.3488 (3) | 0.0913 (3) | 0.5586 (3) | 0.0361 (7) | |
H5N | 0.360 (4) | 0.011 (4) | 0.553 (4) | 0.054* | |
H6N | 0.412 (4) | 0.135 (4) | 0.523 (4) | 0.054* | |
C1 | 0.1978 (4) | 0.5019 (5) | 0.3199 (3) | 0.0384 (8) | |
H1C | 0.310 (4) | 0.530 (3) | 0.357 (3) | 0.046* | |
H2C | 0.173 (4) | 0.505 (4) | 0.223 (3) | 0.046* | |
C2 | 0.1795 (4) | 0.3672 (4) | 0.3563 (3) | 0.0344 (8) | |
H3C | 0.088 (4) | 0.326 (3) | 0.299 (3) | 0.041* | |
H4C | 0.268 (4) | 0.319 (3) | 0.344 (3) | 0.041* | |
C3 | 0.2947 (4) | 0.4550 (3) | 0.7090 (3) | 0.0336 (8) | |
H5C | 0.249 (4) | 0.393 (3) | 0.756 (3) | 0.040* | |
H6C | 0.395 (4) | 0.487 (3) | 0.766 (3) | 0.040* | |
C4 | 0.3208 (3) | 0.3922 (4) | 0.5921 (3) | 0.0336 (8) | |
H7C | 0.373 (4) | 0.463 (3) | 0.553 (3) | 0.040* | |
H8C | 0.392 (4) | 0.325 (3) | 0.612 (3) | 0.040* | |
C5 | 0.1124 (4) | 0.2306 (3) | 0.5155 (3) | 0.0321 (8) | |
H9C | −0.005 (4) | 0.228 (3) | 0.465 (3) | 0.039* | |
H10C | 0.119 (3) | 0.228 (3) | 0.606 (3) | 0.039* | |
C6 | 0.1857 (4) | 0.1147 (4) | 0.4772 (4) | 0.0375 (9) | |
H11C | 0.130 (4) | 0.042 (3) | 0.493 (3) | 0.045* | |
H12C | 0.176 (4) | 0.119 (3) | 0.381 (3) | 0.045* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni | 0.0198 (3) | 0.0282 (3) | 0.0206 (2) | 0.0007 (3) | 0.00450 (19) | 0.0012 (3) |
Cl | 0.0483 (5) | 0.0425 (6) | 0.0569 (6) | −0.0148 (5) | 0.0242 (5) | −0.0105 (5) |
N1 | 0.0301 (16) | 0.0325 (17) | 0.0305 (15) | −0.0024 (13) | 0.0085 (12) | 0.0052 (13) |
N2 | 0.0218 (13) | 0.0330 (15) | 0.0229 (13) | 0.0002 (12) | 0.0033 (10) | −0.0022 (12) |
N3 | 0.0292 (16) | 0.0332 (16) | 0.0234 (13) | −0.0009 (13) | 0.0065 (12) | −0.0018 (13) |
N4 | 0.0340 (16) | 0.0361 (18) | 0.0402 (16) | 0.0052 (14) | 0.0146 (13) | 0.0037 (15) |
C1 | 0.0339 (17) | 0.052 (2) | 0.0339 (16) | 0.004 (2) | 0.0164 (13) | 0.005 (2) |
C2 | 0.0315 (19) | 0.045 (2) | 0.0283 (18) | 0.0036 (18) | 0.0124 (15) | −0.0039 (17) |
C3 | 0.0252 (18) | 0.037 (2) | 0.0301 (16) | 0.0020 (15) | −0.0026 (14) | 0.0017 (15) |
C4 | 0.0172 (16) | 0.044 (2) | 0.0357 (18) | 0.0043 (16) | 0.0028 (14) | −0.0041 (17) |
C5 | 0.0268 (17) | 0.033 (2) | 0.0345 (18) | 0.0020 (15) | 0.0067 (15) | 0.0027 (16) |
C6 | 0.041 (2) | 0.034 (2) | 0.0369 (19) | 0.0016 (17) | 0.0112 (16) | −0.0033 (17) |
Geometric parameters (Å, º) top
Ni—N1 | 2.152 (3) | N4—H6N | 0.90 (4) |
Ni—N2 | 2.176 (3) | C1—C2 | 1.507 (6) |
Ni—N3 | 2.105 (3) | C1—H1C | 1.01 (3) |
Ni—N3i | 2.105 (3) | C1—H2C | 0.99 (3) |
Ni—N1i | 2.152 (3) | C2—H3C | 0.96 (3) |
Ni—N2i | 2.176 (3) | C2—H4C | 0.99 (3) |
N1—C1 | 1.487 (5) | C3—C4 | 1.504 (5) |
N1—H1N | 0.91 (3) | C3—H5C | 0.99 (3) |
N1—H2N | 0.84 (4) | C3—H6C | 0.98 (3) |
N2—C2 | 1.482 (4) | C4—H7C | 1.04 (3) |
N2—C5 | 1.490 (4) | C4—H8C | 0.94 (4) |
N2—C4 | 1.498 (4) | C5—C6 | 1.516 (5) |
N3—C3 | 1.469 (4) | C5—H9C | 1.02 (3) |
N3—H3N | 0.89 (3) | C5—H10C | 0.96 (3) |
N3—H4N | 0.86 (3) | C6—H11C | 0.97 (3) |
N4—C6 | 1.471 (4) | C6—H12C | 1.00 (3) |
N4—H5N | 0.87 (4) | | |
| | | |
N1—Ni—N2 | 80.56 (11) | N1—C1—C2 | 113.0 (3) |
N1i—Ni—N2 | 99.44 (11) | N1—C1—H1C | 109 (2) |
N3i—Ni—N1 | 87.71 (11) | C2—C1—H1C | 111 (2) |
N3—Ni—N1 | 92.29 (11) | N1—C1—H2C | 111 (2) |
N3—Ni—N2 | 82.72 (10) | C2—C1—H2C | 107 (2) |
N3—Ni—N2i | 97.28 (10) | H1C—C1—H2C | 106 (3) |
N3—Ni—N3i | 180.0 | N2—C2—C1 | 111.6 (3) |
N3—Ni—N1i | 87.71 (11) | N2—C2—H3C | 106 (2) |
N3i—Ni—N1i | 92.29 (11) | C1—C2—H3C | 114 (2) |
N1i—Ni—N1 | 180.0 | N2—C2—H4C | 113.8 (19) |
N3i—Ni—N2i | 82.72 (10) | C1—C2—H4C | 107 (2) |
N1i—Ni—N2i | 80.56 (11) | H3C—C2—H4C | 104 (3) |
N1—Ni—N2i | 99.44 (10) | N3—C3—C4 | 110.1 (3) |
N3i—Ni—N2 | 97.28 (10) | N3—C3—H5C | 109 (2) |
N2i—Ni—N2 | 180.0 | C4—C3—H5C | 109 (2) |
C1—N1—Ni | 111.0 (2) | N3—C3—H6C | 110 (2) |
C1—N1—H1N | 108 (2) | C4—C3—H6C | 108.2 (18) |
Ni—N1—H1N | 112 (2) | H5C—C3—H6C | 111 (3) |
C1—N1—H2N | 108 (2) | N2—C4—C3 | 111.1 (3) |
Ni—N1—H2N | 110 (2) | N2—C4—H7C | 108.4 (18) |
H1N—N1—H2N | 108 (3) | C3—C4—H7C | 103.2 (18) |
C2—N2—C5 | 111.8 (3) | N2—C4—H8C | 112 (2) |
C2—N2—C4 | 110.7 (3) | C3—C4—H8C | 116 (2) |
C5—N2—C4 | 112.5 (3) | H7C—C4—H8C | 106 (3) |
C2—N2—Ni | 105.0 (2) | N2—C5—C6 | 118.8 (3) |
C5—N2—Ni | 109.81 (18) | N2—C5—H9C | 106.5 (18) |
C4—N2—Ni | 106.6 (2) | C6—C5—H9C | 107.5 (18) |
C3—N3—Ni | 107.9 (2) | N2—C5—H10C | 107 (2) |
C3—N3—H3N | 107 (2) | C6—C5—H10C | 111 (2) |
Ni—N3—H3N | 109 (2) | H9C—C5—H10C | 105 (2) |
C3—N3—H4N | 110 (2) | N4—C6—C5 | 114.7 (3) |
Ni—N3—H4N | 116 (2) | N4—C6—H11C | 104 (2) |
H3N—N3—H4N | 107 (3) | C5—C6—H11C | 108 (2) |
C6—N4—H5N | 104 (3) | N4—C6—H12C | 110.6 (19) |
C6—N4—H6N | 108 (2) | C5—C6—H12C | 110 (2) |
H5N—N4—H6N | 112 (4) | H11C—C6—H12C | 110 (3) |
| | | |
N3—Ni—N1—C1 | 93.6 (2) | N3i—Ni—N3—C3 | 121 (100) |
N3i—Ni—N1—C1 | −86.4 (2) | N1i—Ni—N3—C3 | 80.4 (2) |
N1i—Ni—N1—C1 | 48 (100) | N1—Ni—N3—C3 | −99.6 (2) |
N2i—Ni—N1—C1 | −168.7 (2) | N2i—Ni—N3—C3 | 160.6 (2) |
N2—Ni—N1—C1 | 11.3 (2) | N2—Ni—N3—C3 | −19.4 (2) |
N3—Ni—N2—C2 | −124.8 (2) | Ni—N1—C1—C2 | 11.3 (3) |
N3i—Ni—N2—C2 | 55.2 (2) | C5—N2—C2—C1 | 166.1 (3) |
N1i—Ni—N2—C2 | 148.7 (2) | C4—N2—C2—C1 | −67.6 (4) |
N1—Ni—N2—C2 | −31.3 (2) | Ni—N2—C2—C1 | 47.1 (3) |
N2i—Ni—N2—C2 | 169 (100) | N1—C1—C2—N2 | −40.2 (4) |
N3—Ni—N2—C5 | 114.8 (2) | Ni—N3—C3—C4 | 43.5 (3) |
N3i—Ni—N2—C5 | −65.2 (2) | C2—N2—C4—C3 | 146.7 (3) |
N1i—Ni—N2—C5 | 28.4 (2) | C5—N2—C4—C3 | −87.4 (3) |
N1—Ni—N2—C5 | −151.6 (2) | Ni—N2—C4—C3 | 33.0 (3) |
N2i—Ni—N2—C5 | 49 (100) | N3—C3—C4—N2 | −52.6 (4) |
N3—Ni—N2—C4 | −7.4 (2) | C2—N2—C5—C6 | 47.0 (4) |
N3i—Ni—N2—C4 | 172.6 (2) | C4—N2—C5—C6 | −78.3 (4) |
N1i—Ni—N2—C4 | −93.8 (2) | Ni—N2—C5—C6 | 163.1 (2) |
N1—Ni—N2—C4 | 86.2 (2) | N2—C5—C6—N4 | 69.7 (4) |
N2i—Ni—N2—C4 | −73 (100) | | |
Symmetry code: (i) −x, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Clii | 0.91 (3) | 2.60 (3) | 3.475 (3) | 162 (3) |
N1—H2N···Cliii | 0.84 (4) | 2.61 (4) | 3.402 (3) | 159 (3) |
N3—H3N···Cliii | 0.89 (4) | 2.40 (4) | 3.284 (3) | 172 (3) |
N3—H4N···N4iv | 0.86 (3) | 2.28 (3) | 3.087 (4) | 156 (3) |
N4—H5N···Clv | 0.87 (4) | 2.57 (4) | 3.432 (3) | 172 (4) |
N4—H6N···Cl | 0.90 (4) | 2.51 (4) | 3.406 (3) | 172 (3) |
Symmetry codes: (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x+1, −y+1, −z+1; (iv) −x+1/2, y+1/2, −z+3/2; (v) −x+1, −y, −z+1. |
(II) bis[tris(2-aminoethyl)amine]nickel(II) tetrathiotungstate
top
Crystal data top
[Ni(C6H18N4)2]WS4 | F(000) = 1320 |
Mr = 663.29 | Dx = 1.978 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.147 (2) Å | Cell parameters from 128 reflections |
b = 11.852 (2) Å | θ = 4–20° |
c = 19.122 (4) Å | µ = 6.40 mm−1 |
β = 104.44 (3)° | T = 293 K |
V = 2227.1 (8) Å3 | Polyhedron, yellow-orange |
Z = 4 | 0.2 × 0.08 × 0.04 mm |
Data collection top
Philips PW 1100 4-circle- diffractometer | 4522 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.019 |
Graphite monochromator | θmax = 28.0°, θmin = 2.7° |
ω–θ scans | h = 0→13 |
Absorption correction: ψ scan X-SHAPE (Stoe & Cie, 1998) and X-RED (Stoe & Cie, 1998) | k = −15→2 |
Tmin = 0.358, Tmax = 0.463 | l = −25→24 |
6750 measured reflections | 4 standard reflections every 120 min |
5386 independent reflections | intensity decay: none |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.021 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.053 | Only H-atom coordinates refined |
S = 1.03 | Calculated w = 1/[σ2(Fo2) + (0.0246P)2 + 1.1404P] where P = (Fo2 + 2Fc2)/3 |
5386 reflections | (Δ/σ)max = 0.002 |
343 parameters | Δρmax = 0.84 e Å−3 |
0 restraints | Δρmin = −0.65 e Å−3 |
Crystal data top
[Ni(C6H18N4)2]WS4 | V = 2227.1 (8) Å3 |
Mr = 663.29 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.147 (2) Å | µ = 6.40 mm−1 |
b = 11.852 (2) Å | T = 293 K |
c = 19.122 (4) Å | 0.2 × 0.08 × 0.04 mm |
β = 104.44 (3)° | |
Data collection top
Philips PW 1100 4-circle- diffractometer | 4522 reflections with I > 2σ(I) |
Absorption correction: ψ scan X-SHAPE (Stoe & Cie, 1998) and X-RED (Stoe & Cie, 1998) | Rint = 0.019 |
Tmin = 0.358, Tmax = 0.463 | 4 standard reflections every 120 min |
6750 measured reflections | intensity decay: none |
5386 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.021 | 0 restraints |
wR(F2) = 0.053 | Only H-atom coordinates refined |
S = 1.03 | Δρmax = 0.84 e Å−3 |
5386 reflections | Δρmin = −0.65 e Å−3 |
343 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
W | 0.208831 (12) | 0.263872 (10) | 0.639058 (6) | 0.02600 (4) | |
Ni | 0.69114 (3) | 0.25185 (3) | 0.381889 (18) | 0.02017 (7) | |
S1 | 0.01227 (10) | 0.18292 (9) | 0.61700 (5) | 0.0498 (2) | |
S2 | 0.22893 (10) | 0.37285 (8) | 0.73337 (5) | 0.0411 (2) | |
S3 | 0.37402 (9) | 0.13706 (7) | 0.66069 (5) | 0.0444 (2) | |
S4 | 0.21983 (10) | 0.36718 (7) | 0.54555 (5) | 0.0417 (2) | |
N1 | 0.7978 (3) | 0.1048 (2) | 0.42911 (15) | 0.0299 (5) | |
H1N | 0.793 (3) | 0.092 (3) | 0.474 (2) | 0.036* | |
H2N | 0.765 (4) | 0.048 (3) | 0.4057 (19) | 0.036* | |
N2 | 0.8559 (2) | 0.2631 (2) | 0.33040 (13) | 0.0243 (5) | |
N3 | 0.5992 (3) | 0.1667 (2) | 0.28322 (14) | 0.0287 (5) | |
H3N | 0.595 (3) | 0.093 (3) | 0.2907 (18) | 0.034* | |
H4N | 0.521 (4) | 0.190 (3) | 0.2664 (19) | 0.034* | |
N4 | 1.1187 (3) | 0.5000 (3) | 0.3448 (2) | 0.0507 (8) | |
H5N | 1.148 (4) | 0.491 (4) | 0.392 (2) | 0.061* | |
H6N | 1.062 (4) | 0.553 (4) | 0.346 (2) | 0.061* | |
N5 | 0.5928 (3) | 0.4036 (2) | 0.33604 (14) | 0.0287 (5) | |
H7N | 0.647 (3) | 0.464 (3) | 0.3365 (18) | 0.034* | |
H8N | 0.558 (4) | 0.392 (3) | 0.291 (2) | 0.034* | |
N6 | 0.5187 (2) | 0.2402 (2) | 0.42811 (13) | 0.0248 (5) | |
N7 | 0.7791 (3) | 0.3383 (2) | 0.48101 (14) | 0.0284 (5) | |
H9N | 0.850 (4) | 0.305 (3) | 0.5061 (19) | 0.034* | |
H10N | 0.799 (3) | 0.403 (3) | 0.4761 (19) | 0.034* | |
N8 | 0.2772 (4) | −0.0069 (3) | 0.4206 (2) | 0.0484 (8) | |
H11N | 0.297 (4) | −0.029 (4) | 0.379 (2) | 0.058* | |
H12N | 0.197 (4) | −0.009 (4) | 0.400 (2) | 0.058* | |
C1 | 0.9396 (3) | 0.1191 (3) | 0.42383 (19) | 0.0349 (7) | |
H1C | 0.996 (4) | 0.048 (3) | 0.4361 (19) | 0.042* | |
H2C | 0.984 (4) | 0.175 (3) | 0.4580 (19) | 0.042* | |
C2 | 0.9370 (3) | 0.1575 (3) | 0.34778 (19) | 0.0331 (7) | |
H3C | 1.023 (4) | 0.176 (3) | 0.3394 (19) | 0.040* | |
H4C | 0.894 (3) | 0.099 (3) | 0.3124 (19) | 0.040* | |
C3 | 0.6805 (3) | 0.1805 (3) | 0.22942 (18) | 0.0361 (7) | |
H5C | 0.623 (4) | 0.205 (3) | 0.187 (2) | 0.043* | |
H6C | 0.721 (4) | 0.114 (3) | 0.2233 (19) | 0.043* | |
C4 | 0.7894 (3) | 0.2705 (3) | 0.25226 (16) | 0.0322 (6) | |
H7C | 0.852 (4) | 0.265 (3) | 0.223 (2) | 0.039* | |
H8C | 0.751 (4) | 0.342 (3) | 0.2403 (19) | 0.039* | |
C5 | 0.9393 (3) | 0.3646 (3) | 0.35566 (17) | 0.0282 (6) | |
H9C | 0.995 (3) | 0.352 (3) | 0.4084 (19) | 0.034* | |
H10C | 0.879 (3) | 0.427 (3) | 0.3526 (18) | 0.034* | |
C6 | 1.0417 (4) | 0.4006 (3) | 0.3134 (2) | 0.0392 (8) | |
H11C | 1.107 (4) | 0.345 (3) | 0.308 (2) | 0.047* | |
H12C | 0.997 (4) | 0.423 (3) | 0.265 (2) | 0.047* | |
C7 | 0.4840 (4) | 0.4312 (3) | 0.3716 (2) | 0.0369 (7) | |
H13C | 0.411 (4) | 0.467 (3) | 0.342 (2) | 0.044* | |
H14C | 0.525 (4) | 0.480 (3) | 0.413 (2) | 0.044* | |
C8 | 0.4189 (3) | 0.3245 (3) | 0.39028 (19) | 0.0327 (7) | |
H15C | 0.352 (4) | 0.343 (3) | 0.4167 (19) | 0.039* | |
H16C | 0.369 (4) | 0.287 (3) | 0.345 (2) | 0.039* | |
C9 | 0.6793 (4) | 0.3488 (4) | 0.5246 (2) | 0.0480 (9) | |
H17C | 0.611 (4) | 0.417 (4) | 0.508 (2) | 0.058* | |
H18C | 0.729 (4) | 0.337 (4) | 0.574 (2) | 0.058* | |
C10 | 0.5700 (4) | 0.2620 (3) | 0.50690 (18) | 0.0401 (8) | |
H19C | 0.495 (4) | 0.272 (3) | 0.531 (2) | 0.048* | |
H20C | 0.625 (4) | 0.187 (3) | 0.529 (2) | 0.048* | |
C11 | 0.4579 (3) | 0.1257 (3) | 0.41681 (19) | 0.0315 (6) | |
H21C | 0.528 (3) | 0.068 (3) | 0.4366 (18) | 0.038* | |
H22C | 0.438 (3) | 0.108 (3) | 0.3657 (19) | 0.038* | |
C12 | 0.3276 (4) | 0.1064 (3) | 0.4406 (2) | 0.0428 (8) | |
H23C | 0.349 (4) | 0.111 (3) | 0.491 (2) | 0.051* | |
H24C | 0.261 (4) | 0.166 (4) | 0.420 (2) | 0.051* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
W | 0.03021 (7) | 0.02242 (6) | 0.02403 (6) | −0.00081 (5) | 0.00424 (4) | 0.00048 (4) |
Ni | 0.02156 (16) | 0.01876 (17) | 0.02060 (16) | 0.00015 (12) | 0.00602 (13) | −0.00127 (12) |
S1 | 0.0450 (5) | 0.0585 (6) | 0.0450 (5) | −0.0151 (4) | 0.0097 (4) | −0.0015 (4) |
S2 | 0.0533 (5) | 0.0360 (4) | 0.0313 (4) | 0.0021 (4) | 0.0058 (4) | −0.0045 (3) |
S3 | 0.0456 (5) | 0.0314 (4) | 0.0478 (5) | 0.0097 (4) | −0.0042 (4) | −0.0051 (4) |
S4 | 0.0613 (6) | 0.0329 (4) | 0.0341 (4) | −0.0009 (4) | 0.0179 (4) | 0.0061 (3) |
N1 | 0.0369 (14) | 0.0209 (12) | 0.0324 (14) | 0.0017 (10) | 0.0097 (12) | 0.0020 (10) |
N2 | 0.0253 (11) | 0.0243 (12) | 0.0246 (11) | −0.0023 (9) | 0.0085 (9) | −0.0027 (9) |
N3 | 0.0259 (12) | 0.0313 (14) | 0.0284 (13) | −0.0047 (11) | 0.0061 (10) | −0.0049 (10) |
N4 | 0.0438 (19) | 0.0419 (19) | 0.071 (2) | −0.0165 (14) | 0.0227 (18) | −0.0084 (17) |
N5 | 0.0320 (13) | 0.0245 (13) | 0.0307 (13) | 0.0010 (10) | 0.0097 (11) | 0.0048 (10) |
N6 | 0.0252 (11) | 0.0261 (12) | 0.0240 (11) | −0.0004 (9) | 0.0079 (9) | 0.0008 (9) |
N7 | 0.0302 (13) | 0.0280 (13) | 0.0265 (12) | −0.0035 (11) | 0.0061 (10) | −0.0029 (10) |
N8 | 0.0417 (17) | 0.0440 (18) | 0.060 (2) | −0.0126 (15) | 0.0135 (16) | 0.0036 (15) |
C1 | 0.0335 (17) | 0.0298 (16) | 0.0389 (17) | 0.0066 (13) | 0.0043 (14) | 0.0030 (13) |
C2 | 0.0307 (16) | 0.0270 (15) | 0.0447 (18) | 0.0036 (12) | 0.0151 (14) | −0.0035 (13) |
C3 | 0.0323 (17) | 0.048 (2) | 0.0289 (15) | −0.0036 (14) | 0.0099 (13) | −0.0125 (14) |
C4 | 0.0317 (15) | 0.0420 (18) | 0.0248 (14) | −0.0061 (14) | 0.0106 (12) | −0.0034 (13) |
C5 | 0.0255 (14) | 0.0276 (15) | 0.0316 (15) | −0.0049 (12) | 0.0076 (12) | −0.0032 (12) |
C6 | 0.0324 (17) | 0.043 (2) | 0.046 (2) | −0.0110 (15) | 0.0169 (15) | −0.0059 (16) |
C7 | 0.0351 (17) | 0.0291 (16) | 0.049 (2) | 0.0092 (13) | 0.0148 (15) | 0.0055 (14) |
C8 | 0.0252 (15) | 0.0334 (17) | 0.0417 (18) | 0.0057 (12) | 0.0124 (14) | 0.0052 (14) |
C9 | 0.047 (2) | 0.065 (3) | 0.0340 (18) | −0.0135 (19) | 0.0145 (16) | −0.0162 (18) |
C10 | 0.0391 (17) | 0.058 (2) | 0.0263 (15) | −0.0104 (16) | 0.0144 (13) | −0.0049 (15) |
C11 | 0.0303 (16) | 0.0277 (15) | 0.0384 (17) | −0.0015 (12) | 0.0123 (13) | 0.0025 (13) |
C12 | 0.0405 (19) | 0.0385 (19) | 0.054 (2) | −0.0077 (15) | 0.0212 (17) | 0.0025 (17) |
Geometric parameters (Å, º) top
W—S1 | 2.1580 (10) | N8—H11N | 0.91 (4) |
W—S2 | 2.1860 (9) | N8—H12N | 0.81 (4) |
W—S3 | 2.2122 (9) | C1—C2 | 1.518 (5) |
W—S4 | 2.1929 (9) | C1—H1C | 1.01 (4) |
Ni—N1 | 2.130 (3) | C1—H2C | 0.96 (4) |
Ni—N2 | 2.146 (2) | C2—H3C | 0.95 (4) |
Ni—N3 | 2.138 (3) | C2—H4C | 0.99 (4) |
Ni—N5 | 2.136 (3) | C3—C4 | 1.519 (5) |
Ni—N6 | 2.152 (2) | C3—H5C | 0.93 (4) |
Ni—N7 | 2.143 (3) | C3—H6C | 0.91 (4) |
N1—C1 | 1.477 (4) | C4—H7C | 0.95 (4) |
N1—H1N | 0.87 (4) | C4—H8C | 0.94 (4) |
N1—H2N | 0.83 (4) | C5—C6 | 1.528 (4) |
N2—C5 | 1.480 (4) | C5—H9C | 1.04 (3) |
N2—C4 | 1.481 (4) | C5—H10C | 0.95 (3) |
N2—C2 | 1.489 (4) | C6—H11C | 0.96 (4) |
N3—C3 | 1.480 (4) | C6—H12C | 0.97 (4) |
N3—H3N | 0.89 (4) | C7—C8 | 1.510 (5) |
N3—H4N | 0.83 (4) | C7—H13C | 0.91 (4) |
N4—C6 | 1.457 (5) | C7—H14C | 0.98 (4) |
N4—H5N | 0.88 (4) | C8—H15C | 0.97 (4) |
N4—H6N | 0.86 (4) | C8—H16C | 0.99 (4) |
N5—C7 | 1.471 (4) | C9—C10 | 1.488 (5) |
N5—H7N | 0.90 (4) | C9—H17C | 1.06 (4) |
N5—H8N | 0.86 (4) | C9—H18C | 0.96 (4) |
N6—C8 | 1.477 (4) | C10—H19C | 0.99 (4) |
N6—C11 | 1.485 (4) | C10—H20C | 1.08 (4) |
N6—C10 | 1.489 (4) | C11—C12 | 1.519 (4) |
N7—C9 | 1.468 (4) | C11—H21C | 0.99 (4) |
N7—H9N | 0.86 (4) | C11—H22C | 0.97 (3) |
N7—H10N | 0.80 (4) | C12—H23C | 0.94 (4) |
N8—C12 | 1.454 (5) | C12—H24C | 0.99 (4) |
| | | |
S1—W—S2 | 108.39 (4) | H1C—C1—H2C | 106 (3) |
S1—W—S3 | 110.78 (4) | N2—C2—C1 | 110.0 (2) |
S1—W—S4 | 108.75 (5) | N2—C2—H3C | 104 (2) |
S2—W—S3 | 109.68 (4) | C1—C2—H3C | 116 (2) |
S2—W—S4 | 109.24 (4) | N2—C2—H4C | 108 (2) |
S4—W—S3 | 109.97 (4) | C1—C2—H4C | 110 (2) |
N1—Ni—N2 | 82.75 (10) | H3C—C2—H4C | 108 (3) |
N1—Ni—N3 | 92.96 (11) | N3—C3—C4 | 111.7 (3) |
N1—Ni—N5 | 177.34 (11) | N3—C3—H5C | 108 (2) |
N1—Ni—N6 | 98.77 (10) | C4—C3—H5C | 106 (2) |
N1—Ni—N7 | 87.74 (11) | N3—C3—H6C | 110 (2) |
N3—Ni—N2 | 80.95 (10) | C4—C3—H6C | 109 (2) |
N5—Ni—N2 | 95.56 (10) | H5C—C3—H6C | 112 (3) |
N2—Ni—N6 | 177.05 (9) | N2—C4—C3 | 111.4 (3) |
N7—Ni—N2 | 100.13 (10) | N2—C4—H7C | 113 (2) |
N5—Ni—N3 | 88.79 (11) | C3—C4—H7C | 109 (2) |
N3—Ni—N6 | 96.42 (10) | N2—C4—H8C | 111 (2) |
N3—Ni—N7 | 178.78 (10) | C3—C4—H8C | 110 (2) |
N5—Ni—N6 | 83.01 (9) | H7C—C4—H8C | 102 (3) |
N5—Ni—N7 | 90.54 (11) | N2—C5—C6 | 117.6 (3) |
N7—Ni—N6 | 82.49 (10) | N2—C5—H9C | 109.0 (19) |
C1—N1—Ni | 106.11 (19) | C6—C5—H9C | 106.3 (19) |
C1—N1—H1N | 112 (2) | N2—C5—H10C | 108 (2) |
Ni—N1—H1N | 114 (2) | C6—C5—H10C | 105 (2) |
C1—N1—H2N | 109 (2) | H9C—C5—H10C | 111 (3) |
Ni—N1—H2N | 110 (3) | N4—C6—C5 | 111.9 (3) |
H1N—N1—H2N | 106 (3) | N4—C6—H11C | 107 (2) |
C5—N2—C4 | 111.2 (2) | C5—C6—H11C | 116 (2) |
C5—N2—C2 | 111.8 (2) | N4—C6—H12C | 104 (2) |
C4—N2—C2 | 111.2 (2) | C5—C6—H12C | 112 (2) |
C5—N2—Ni | 110.36 (17) | H11C—C6—H12C | 104 (3) |
C4—N2—Ni | 104.81 (17) | N5—C7—C8 | 110.2 (3) |
C2—N2—Ni | 107.19 (18) | N5—C7—H13C | 113 (2) |
C3—N3—Ni | 111.42 (19) | C8—C7—H13C | 102 (2) |
C3—N3—H3N | 106 (2) | N5—C7—H14C | 107 (2) |
Ni—N3—H3N | 110 (2) | C8—C7—H14C | 115 (2) |
C3—N3—H4N | 110 (2) | H13C—C7—H14C | 110 (3) |
Ni—N3—H4N | 111 (3) | N6—C8—C7 | 113.3 (3) |
H3N—N3—H4N | 108 (3) | N6—C8—H15C | 113 (2) |
C6—N4—H5N | 110 (3) | C7—C8—H15C | 110 (2) |
C6—N4—H6N | 108 (3) | N6—C8—H16C | 105 (2) |
H5N—N4—H6N | 96 (4) | C7—C8—H16C | 109 (2) |
C7—N5—Ni | 108.98 (19) | H15C—C8—H16C | 106 (3) |
C7—N5—H7N | 111 (2) | N7—C9—C10 | 113.1 (3) |
Ni—N5—H7N | 116 (2) | N7—C9—H17C | 113 (2) |
C7—N5—H8N | 109 (2) | C10—C9—H17C | 94 (2) |
Ni—N5—H8N | 108 (2) | N7—C9—H18C | 106 (2) |
H7N—N5—H8N | 104 (3) | C10—C9—H18C | 108 (3) |
C8—N6—C11 | 109.8 (2) | H17C—C9—H18C | 123 (3) |
C8—N6—C10 | 113.7 (3) | C9—C10—N6 | 113.7 (3) |
C11—N6—C10 | 109.5 (2) | C9—C10—H19C | 116 (2) |
C8—N6—Ni | 106.48 (18) | N6—C10—H19C | 112 (2) |
C11—N6—Ni | 110.46 (18) | C9—C10—H20C | 101 (2) |
C10—N6—Ni | 106.82 (18) | N6—C10—H20C | 106 (2) |
C9—N7—Ni | 110.4 (2) | H19C—C10—H20C | 107 (3) |
C9—N7—H9N | 109 (2) | N6—C11—C12 | 117.1 (3) |
Ni—N7—H9N | 113 (2) | N6—C11—H21C | 110 (2) |
C9—N7—H10N | 102 (3) | C12—C11—H21C | 112 (2) |
Ni—N7—H10N | 114 (3) | N6—C11—H22C | 109 (2) |
H9N—N7—H10N | 108 (3) | C12—C11—H22C | 107 (2) |
C12—N8—H11N | 111 (3) | H21C—C11—H22C | 101 (3) |
C12—N8—H12N | 113 (3) | N8—C12—C11 | 109.6 (3) |
H11N—N8—H12N | 89 (4) | N8—C12—H23C | 107 (3) |
N1—C1—C2 | 108.4 (3) | C11—C12—H23C | 108 (2) |
N1—C1—H1C | 113 (2) | N8—C12—H24C | 113 (2) |
C2—C1—H1C | 110 (2) | C11—C12—H24C | 110 (2) |
N1—C1—H2C | 110 (2) | H23C—C12—H24C | 109 (3) |
C2—C1—H2C | 110 (2) | | |
| | | |
N5—Ni—N1—C1 | −29 (2) | N2—Ni—N6—C11 | 70.6 (18) |
N3—Ni—N1—C1 | 101.9 (2) | N1—Ni—N6—C10 | 68.7 (2) |
N7—Ni—N1—C1 | −79.1 (2) | N5—Ni—N6—C10 | −109.3 (2) |
N2—Ni—N1—C1 | 21.4 (2) | N3—Ni—N6—C10 | 162.7 (2) |
N6—Ni—N1—C1 | −161.2 (2) | N7—Ni—N6—C10 | −17.9 (2) |
N1—Ni—N2—C5 | −114.2 (2) | N2—Ni—N6—C10 | −170.4 (17) |
N5—Ni—N2—C5 | 63.7 (2) | N1—Ni—N7—C9 | −101.8 (3) |
N3—Ni—N2—C5 | 151.6 (2) | N5—Ni—N7—C9 | 80.2 (3) |
N7—Ni—N2—C5 | −27.9 (2) | N3—Ni—N7—C9 | 24 (5) |
N6—Ni—N2—C5 | 124.5 (17) | N2—Ni—N7—C9 | 176.0 (3) |
N1—Ni—N2—C4 | 126.0 (2) | N6—Ni—N7—C9 | −2.7 (3) |
N5—Ni—N2—C4 | −56.1 (2) | Ni—N1—C1—C2 | −46.8 (3) |
N3—Ni—N2—C4 | 31.82 (19) | C5—N2—C2—C1 | 85.5 (3) |
N7—Ni—N2—C4 | −147.61 (19) | C4—N2—C2—C1 | −149.6 (3) |
N6—Ni—N2—C4 | 4.7 (19) | Ni—N2—C2—C1 | −35.5 (3) |
N1—Ni—N2—C2 | 7.7 (2) | N1—C1—C2—N2 | 56.7 (3) |
N5—Ni—N2—C2 | −174.35 (19) | Ni—N3—C3—C4 | −12.1 (4) |
N3—Ni—N2—C2 | −86.5 (2) | C5—N2—C4—C3 | −167.5 (3) |
N7—Ni—N2—C2 | 94.1 (2) | C2—N2—C4—C3 | 67.2 (3) |
N6—Ni—N2—C2 | −113.5 (18) | Ni—N2—C4—C3 | −48.3 (3) |
N1—Ni—N3—C3 | −93.3 (2) | N3—C3—C4—N2 | 41.3 (4) |
N5—Ni—N3—C3 | 84.7 (2) | C4—N2—C5—C6 | −51.2 (4) |
N7—Ni—N3—C3 | 141 (5) | C2—N2—C5—C6 | 73.8 (4) |
N2—Ni—N3—C3 | −11.1 (2) | Ni—N2—C5—C6 | −167.0 (2) |
N6—Ni—N3—C3 | 167.5 (2) | N2—C5—C6—N4 | −178.8 (3) |
N1—Ni—N5—C7 | −120 (2) | Ni—N5—C7—C8 | −34.9 (3) |
N3—Ni—N5—C7 | 109.0 (2) | C11—N6—C8—C7 | −155.7 (3) |
N7—Ni—N5—C7 | −70.0 (2) | C10—N6—C8—C7 | 81.2 (3) |
N2—Ni—N5—C7 | −170.3 (2) | Ni—N6—C8—C7 | −36.1 (3) |
N6—Ni—N5—C7 | 12.3 (2) | N5—C7—C8—N6 | 49.2 (4) |
N1—Ni—N6—C8 | −169.5 (2) | Ni—N7—C9—C10 | 23.6 (4) |
N5—Ni—N6—C8 | 12.5 (2) | N7—C9—C10—N6 | −41.5 (5) |
N3—Ni—N6—C8 | −75.4 (2) | C8—N6—C10—C9 | −80.5 (4) |
N7—Ni—N6—C8 | 104.0 (2) | C11—N6—C10—C9 | 156.3 (3) |
N2—Ni—N6—C8 | −48.6 (19) | Ni—N6—C10—C9 | 36.6 (4) |
N1—Ni—N6—C11 | −50.3 (2) | C8—N6—C11—C12 | −57.7 (4) |
N5—Ni—N6—C11 | 131.7 (2) | C10—N6—C11—C12 | 67.8 (4) |
N3—Ni—N6—C11 | 43.7 (2) | Ni—N6—C11—C12 | −174.8 (3) |
N7—Ni—N6—C11 | −136.8 (2) | N6—C11—C12—N8 | 175.7 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N8i | 0.87 (4) | 2.52 (4) | 3.358 (4) | 161 (3) |
N1—H2N···S3i | 0.83 (4) | 2.75 (4) | 3.565 (3) | 171 (3) |
N3—H3N···S3i | 0.89 (4) | 2.87 (4) | 3.747 (3) | 169 (3) |
N3—H4N···S2ii | 0.83 (4) | 2.97 (4) | 3.669 (3) | 144 (3) |
N3—H4N···S3ii | 0.83 (4) | 3.00 (4) | 3.667 (3) | 139 (3) |
N5—H7N···S2iii | 0.90 (4) | 2.82 (4) | 3.640 (3) | 152 (3) |
N5—H8N···S3ii | 0.86 (4) | 2.73 (4) | 3.562 (3) | 162 (3) |
N7—H9N···S1iv | 0.86 (4) | 2.75 (4) | 3.561 (3) | 158 (3) |
N7—H10N···S4iii | 0.80 (4) | 2.76 (4) | 3.528 (3) | 162 (3) |
N8—H12N···S1v | 0.81 (4) | 2.92 (5) | 3.528 (3) | 133 (4) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, −y+1/2, z−1/2; (iii) −x+1, −y+1, −z+1; (iv) x+1, y, z; (v) −x, −y, −z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Ni(C6H18N4)2]Cl2 | [Ni(C6H18N4)2]WS4 |
Mr | 422.10 | 663.29 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 9.0336 (18), 10.630 (2), 10.717 (2) | 10.147 (2), 11.852 (2), 19.122 (4) |
β (°) | 108.78 (3) | 104.44 (3) |
V (Å3) | 974.3 (3) | 2227.1 (8) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.28 | 6.40 |
Crystal size (mm) | 0.5 × 0.1 × 0.1 | 0.2 × 0.08 × 0.04 |
|
Data collection |
Diffractometer | STOE AED-II four-circle diffractometer | Philips PW 1100 4-circle- diffractometer |
Absorption correction | ψ scan X-SHAPE (Stoe & Cie, 1998) and X-RED (Stoe & Cie, 1998) | ψ scan X-SHAPE (Stoe & Cie, 1998) and X-RED (Stoe & Cie, 1998) |
Tmin, Tmax | 0.810, 0.840 | 0.358, 0.463 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2042, 1715, 1131 | 6750, 5386, 4522 |
Rint | 0.034 | 0.019 |
(sin θ/λ)max (Å−1) | 0.595 | 0.661 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.073, 1.01 | 0.021, 0.053, 1.03 |
No. of reflections | 1715 | 5386 |
No. of parameters | 160 | 343 |
H-atom treatment | Only H-atom coordinates refined | Only H-atom coordinates refined |
Δρmax, Δρmin (e Å−3) | 0.28, −0.27 | 0.84, −0.65 |
Selected geometric parameters (Å, º) for (I) topNi—N1 | 2.152 (3) | Ni—N3 | 2.105 (3) |
Ni—N2 | 2.176 (3) | | |
| | | |
N1—Ni—N2 | 80.56 (11) | N3—Ni—N1 | 92.29 (11) |
N1i—Ni—N2 | 99.44 (11) | N3—Ni—N2 | 82.72 (10) |
N3i—Ni—N1 | 87.71 (11) | N3—Ni—N2i | 97.28 (10) |
Symmetry code: (i) −x, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Clii | 0.91 (3) | 2.60 (3) | 3.475 (3) | 162 (3) |
N1—H2N···Cliii | 0.84 (4) | 2.61 (4) | 3.402 (3) | 159 (3) |
N3—H3N···Cliii | 0.89 (4) | 2.40 (4) | 3.284 (3) | 172 (3) |
N3—H4N···N4iv | 0.86 (3) | 2.28 (3) | 3.087 (4) | 156 (3) |
N4—H5N···Clv | 0.87 (4) | 2.57 (4) | 3.432 (3) | 172 (4) |
N4—H6N···Cl | 0.90 (4) | 2.51 (4) | 3.406 (3) | 172 (3) |
Symmetry codes: (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x+1, −y+1, −z+1; (iv) −x+1/2, y+1/2, −z+3/2; (v) −x+1, −y, −z+1. |
Selected geometric parameters (Å, º) for (II) topW—S1 | 2.1580 (10) | Ni—N2 | 2.146 (2) |
W—S2 | 2.1860 (9) | Ni—N3 | 2.138 (3) |
W—S3 | 2.2122 (9) | Ni—N5 | 2.136 (3) |
W—S4 | 2.1929 (9) | Ni—N6 | 2.152 (2) |
Ni—N1 | 2.130 (3) | Ni—N7 | 2.143 (3) |
| | | |
S1—W—S2 | 108.39 (4) | N3—Ni—N2 | 80.95 (10) |
S1—W—S3 | 110.78 (4) | N5—Ni—N2 | 95.56 (10) |
S1—W—S4 | 108.75 (5) | N2—Ni—N6 | 177.05 (9) |
S2—W—S3 | 109.68 (4) | N7—Ni—N2 | 100.13 (10) |
S2—W—S4 | 109.24 (4) | N5—Ni—N3 | 88.79 (11) |
S4—W—S3 | 109.97 (4) | N3—Ni—N6 | 96.42 (10) |
N1—Ni—N2 | 82.75 (10) | N3—Ni—N7 | 178.78 (10) |
N1—Ni—N3 | 92.96 (11) | N5—Ni—N6 | 83.01 (9) |
N1—Ni—N5 | 177.34 (11) | N5—Ni—N7 | 90.54 (11) |
N1—Ni—N6 | 98.77 (10) | N7—Ni—N6 | 82.49 (10) |
N1—Ni—N7 | 87.74 (11) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N8i | 0.87 (4) | 2.52 (4) | 3.358 (4) | 161 (3) |
N1—H2N···S3i | 0.83 (4) | 2.75 (4) | 3.565 (3) | 171 (3) |
N3—H3N···S3i | 0.89 (4) | 2.87 (4) | 3.747 (3) | 169 (3) |
N5—H7N···S2ii | 0.90 (4) | 2.82 (4) | 3.640 (3) | 152 (3) |
N5—H8N···S3iii | 0.86 (4) | 2.73 (4) | 3.562 (3) | 162 (3) |
N7—H9N···S1iv | 0.86 (4) | 2.75 (4) | 3.561 (3) | 158 (3) |
N7—H10N···S4ii | 0.80 (4) | 2.76 (4) | 3.528 (3) | 162 (3) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x, −y+1/2, z−1/2; (iv) x+1, y, z. |
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It is well documented that the tren molecule can act as a tri- or tetradentate ligand and several transition metal complexes have been prepared (Gaudin et al., 1986). Many transition metal ions prefer the octahedral geometry with tren as a tetradentate ligand, leaving two cis positions available for bonding to other ligands. Examples are [Ni(tren)(H2O)Cl]Cl·H2O (Marzotto et al., 1993) and [Ni(tren){N(CN)2}2] (Březina et al., 1999). If the two cis positions are used by another multidentate ligand, such as the oxalate anion. dimeric complexes were obtained, with the two Ni(tren) units bridged by the other multidentate ligand, as in [Ni2(tren)2(C2O4)](ClO4)2 (Castro et al., 1997; Březina et al., 1997) and [Ni2(tren)2(C6O4Cl2)](BPh4)2 (Pierpont et al., 1977). Another binding mode of the tren ligand yields cationic chains. These chains are found in the two compounds {[Ni2(tren)3](ClO4)4·H2O}n (Masters et al., 1999) and {[Ni2(tren)3][Mo2O2S6]2·2.75H2O}n (Ellermeier & Bensch, 2001). In the polymeric chains, one Ni atom is coordinated by two tren molecules which act as tridentate ligands. The other Ni atom is coordinated by all four N atoms of one tren molecule and by the two remaining N atoms of the two tren ligands which are tridentate bound to the neighboured Ni atoms. The coordination behavior of the tren molecules leads to the formation of zigzag [Ni2(tren)3]n chains. The two new [Ni(tren)2]2+ complexes presented here contain isolated cations with the tren molecules acting as a tridentate ligand. This coordination mode was first reported by Colpas et al. (1990) for [Ni(tren)2](BF4)2.
Violet crystals of [Ni(tren)2]Cl2, (I), were obtained by attempts to synthesize compounds which could be used as precursors for the syntheses of new thioantimonates with complex transition metal cations (Stähler & Bensch, 2001). Due to the abovementioned variety in the bonding modes of the multidentate tren molecule, a single-crystal diffraction study was performed. In contrast, [Ni(tren)2]WS4, (II), was obtained as part of a project on the synthesis of new thiotungstates with transition metals under solvothermal conditions. Both compounds contain the [Ni(tren)2]2+ complex cation, and the counter-ions are Cl- in (I) and the tetrahedral [WS4]2- anion in (II). Each Ni2+ cation in [Ni(tren)2]2+ in (I) and (II) is sixfold coordinated by the N atoms of two tren molecules acting as tridentate ligands. Therefore, each tren ligand has one primary amine group which is not connected to the transition metal atom. The structures of the cations in (I) and (II) are illustrated in Figs. 1 and 2, and selected bond lengths and angles are given in Tables 1 and 3, respectively. In (I), the Ni atom is on a centre of inversion, surrounded by one crystallographically independent tren molecule. The environment is completed by a tren molecule generated by symmetry. In (II), the Ni atom is bound to two crystallographically independent tren molecules. The Ni—N bond lengths in (I) are between 2.105 (3) and 2.176 (3) Å. The N—Ni—N angles range from 80.56 (11) to 99.44 (11)°, reflecting the distortion of the octahedral geometry. The chloride anions in (I) are involved in a complicated hydrogen-bond network (Table 2) that may significantly contribute to the stability of the compound. There are five short intermolecular contacts between the Cl- anions and the H atoms of the tren ligand ranging from 2.40 (4) (H3N···Clii) to 2.61 (4) Å [H2N···Clii; symmetry code: (ii) -x, -y, -z]. A short contact is also observed between an H atom and an N atom of neighbouring tren molecules [H4N···N4iii; symmetry code: (iii) -x + 1/2, y + 1/2, -z + 3/2].
The WS4 tetrahedron in compound (II) is only slightly distorted (Fig. 2), with S—W—S angles between 108.39 (4) and 110.78 (4)° (Table 3). The W—S bond lengths range from 2.1580 (10) to 2.2122 (9) Å. The W—S3 distance of 2.2122 (9) Å is significantly longer than the average W—S bond length in [WS4]2- anions of 2.177 Å (Müller et al., 1981). One reason may be that S3 is involved in three short contacts to H atoms of the tren ligands (Table 4). The other S atoms have only one relatively short contact to H atoms. The geometrical parameters for the [Ni(tren)2]2+ cation in (II) are in good agreement with that found in the cation of (I) and with the [Ni(tren)2]2+ cation described by Colpas et al. (1990). The Ni—N bond lengths vary from 2.130 (3) to 2.152 (2) Å and the corresponding cis-N—Ni—N angles range from 80.95 (10) to 100.13 (10)° (Table 3). The [WS4]2- anions and [Ni(tren)2]2+ cations in (II) each form rods along the a and c axes and the rods alterante along the b axis (Fig. 3).